Gallium containing cations

Inclusion of these cations does impart new catalytic activities, but in many cases the active site results from a metal ion that has left the framework and entered the pore space upon heating, especially in the presence of water vapour. This is thought to be the case for zinc- and gallium-containing solids used in the dehydrocyclisation of butane and propane to aromatics in the Cyclar process (Chapter 9). Boron, iron, chromium and vanadium all appear to leave the framework under harsh conditions. The incorporation of titanium and more recently tin into framework sites within silicates have become very important substitutions, because both titanosilicates and stannosilicates have been shown to contain stable Lewis acid sites of importance in selective oxidation catalysis. The metal atom can coordinate additional water molecules in the as-prepared material, but these can be removed by heating. In the synthesis of titanosilicates, titanium is usually added to the gel as the alkoxide, and synthesis performed in the absence of sodium hydroxide to avoid precipitation of sodium titanate or nanoparticulate titanium oxides. 

The same disciission may apply to the anodic dissolution of semiconductor electrodes of covalently bonded compounds such as gallium arsenide. In general, covalent compoimd semiconductors contain varying ionic polarity, in which the component atoms of positive polarity re likely to become surface cations and the component atoms of negative polarity are likely to become surface radicals. For such compound semiconductors in anodic dissolution, the valence band mechanism predominates over the conduction band mechanism with increasing band gap and increasing polarity of the compounds. 

In addition to the results on porosils given above, the cobalticinium cation has also been applied to the synthesis of microporous solids of other host compositions. Balkus et al. have described their results for the synthesis of open-framework aluminophosphates, [54] and Kallus et al. have determined the structure of a cobalticinium-containing gallium phosphate. This compound, however, is not a true zeotype since it does not possess a three-dimensional framework structure [55]. 

Table 1. Metal-molten salt systems in which solid, sub-valent compounds with metal-metal bonds have been synthesized by symproportionation or similar reactions. The many sub-halides of gallium and indium have been omitted. These compounds contain either sub-valent monoatomic cations e.Lj. (Ga )(GaCl4 )l > and (In )(Cl )] " and/or ligand-stabilized metal-metal bonded anions (Ga+)2(Ga2X6- ), X = Br, For a review of the sub-valent chemistry of the group...

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